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Patented ll,

"entree ALBERT BUDMER, F WATTVJ'IL, SWITZERLAND, ASSIGNOR T0 HEBEELEIN db 39.,

A. Ga, 01F WAT'E'WHI, SWTEZERLAND, A CQEPQRATIQN 0F Sl/VIEZEELAND.

' DYEIEBIG.

No Drawing. Application filed Tuly 10, 1926, Serial Ito, 121,?36, and in Germany July 1%, 1925.

My invention relates to improvements in dyeing and more particularly the main object of the invention is to provide an improved method for treating cellulosic fibers or fab- 5 rice to render the same relatively immune to substantive dyestufls and also certain novel products which may be produced with the' methods have certain disadvantages. A0

cording to the present invention in its pre-- ferred form the vegetable or cellulosic fibers so or fabric are treated with a phosphorous halogen compound whereby novel and valuable products are obtained. In addition to purely inorganic phosphorous halogen compounds such as phosphorous trichloride, phosphorous .oxychloride, etc. organically substituted phosphorous halogen compounds such as ethylphospho-oxy-chloride and other phosphorous compounds such as triphenylphosphate may be used with more or less success.

@ne method of carrying out certain features of the invention is as follows. Cotton yarn is immersed in a solution of caustic soda in alcohol, containing 10% of caustic soda, to alkalize the cellulosic fibers thereof in a manner well understood by those skilled in the art, and after removing the yarn'from' the solution the excess of solution is squeezed out of the same. The yarn thus prepared is then brought into a solution of phosphor ous trichloride in xylol containing 200 grams of phosphorous trichloride perliter of Xylol. Thus the cotton fibers of the yarn are treated with the phosphorous halogen compound in the presence of some alkali which remains on the yarn from the a1ka1izing treatment. When the yarn is thus treated with the phosphorous trichloride'solution the reaction takes place after a short time, with some warming. The yarn is then thoroughly washed and dried and it is found that the fibers have lost their aity for and are substantially immune to substantive dyestufi'swhile they have acquired a pronounced capacity for dyeing with basic dyestufis wlthout previous mordanting.

The yarn so treated may be woven" together with ordinary cotton yarn or untreated cellulosic threads to'form a fabric and remains in the fabric as a white vefi ect when the fabric is dyed with substantive dyestufis. llf desired, the yarn before the treatment with the phosphorous compound, may be colored, as forexarn le with sub-- stantive dyestufi, and then rendered immune 6a to further dyeing with substantive dyestuffs by the treatment as above described and then the yarn woven together with untreated cotton yarn or cellulosic threads,'and the fabric treated with a'substantive dyestufi' of a different color, whereupon the threads which have been treated with the phosphorous compound will remain of a difi'erent color from those which were untreated with the phosphorous compound. The reaction it of the phosphorous halogen compound on the cellulous appears to set free halogen acid andthe presence of alkali on the goods will serve to remove such acideby neutralizing the same thus preventin its injuring the goods. The phosphorus believe combines with the cellulosic material to form a phosphorous cellulose compound which is relatively resistant and immune to substantive dyestuffs and relatively attractive to basic dyestufis, generally speaking.

i Instead of treating the yarn before it is woven into fabric, a woven fabric made of cotton or cellulosic fibres may be first treated with an aqueous caustic alkali solution in the well known way to alkalize the cellulose thereof and then the excess alkali solution squeezed out and the fabric passed "through a 10% solution of phosphorous oxychloride in' benzol. "Various other hydrocarbon solvents maybe used fill for producing the solution of the phosphoras artificial silk made from regenerated cellulose, e. g. hydracellulose such as viscose, cupra ammonia cellulose and collodion silk. Such artificial silk may be treated with the phosphorous compounds as above described and it will then be found to have become substantially immune to substantive dyestuffs and to have acquired an affinity and attraction for basic dyestuffs. Therefore, by cellulosic fibers, and fabrics or material I intend to include all such artificial silk as well as other cellulosic material. .VVith artificial silks which consist of cellulose esters or cellulose ethers e. g. acetate silk, and which repel most of the common dyestuffs, their afiinity for basic dyetsuifs becomes marked when treated in the manner described.

The treatment with alkali may be applied after instead of before the treatment with the phosphorous compound. Thus it is not reaction, acid binding necessary that the cellulosic material be treatedwith the phosphorous compound in the presence of the alkali and the cellulosic material may be washed with water or with an inert solvent and dried, if desired, between the two treatments. Also in many cases the alkali treatment may be omitted altogether and substantially the same results obtained.

The cellulosic material may be directl treated with the phosphorous compoun and without any treatment with alkali, and there may, according to the concentration, be embodied in the fiber or added to the solution to neutralize the acid liberated in the or removing bodies such as sodium bicarbonate, calcium carbonate and the like. This method is also not only applicable to the natural cellulose fililers but also to the artificial silks and the li e.

White and colored or two colored effects may also be produced in a fabric by the local application or treatment to render oer tain portions of the cellulosic material immune to substantive dyestuffs and attractive to basic dyestuffs according to any predetermined design. Thus a reserve thickening or paste may be printed upon the fabric according to the predetermined design and then the fabric treated with the phosphorous compound solution either with previous alkalization or subsequent alkalization or without the same. Thus the treatment may. be carried out either in the presence or absence of alkali. If desired the alkalization of the fiber may accomplished by printing a thickened alkali directly on the fabric in accordance with a predetermined design and then the local chemical changes brought about by immersion of the fabric in the solution of phosphorous compound and if desired a dyestufi may be printed on the fabric at the same time with the thickened alkali,

or a thickened solution of the phosphorous compound may be printed on'the fabric according to a predetermined design.

Thus the process. may be used for the production of new materials of natural vegetable or artificial fibers, with pattern effects by the local application of the phosphorous compound by printing or applying the same in accordance with any predetermined design, whereupon the portions so acted upon by-the phosphorous compound will be particularly resistant to substantive dyestuffs and relatively attractive to basic dyestuffs and upon subsequent dyeing, clouded or other variegated effects may be-produced. While a phosphorous chlorine compound is preferred, nevertheless other halogens and other compounds of phosphorus may be used with more or less success.

While I have described my improvements in great detail and with respect to preferred forms thereof, I do not desire to be limited to such details or forms since many modifications and changes may be made and the invention embodied in widely different forms without departing from the spirit and scope thereof in its broader aspects. Hence I desire to cover all modifications and forms coming within the language or scope of any one or more of the appended claims.

What I claim as new and desire to secure by Letters Patent, is: s

1. Method of modifying the dyeing properties of cellulosic fibers which consists in acting on the same with a phosphorous com pound capable of making the cellulosic fibers relatively immune to substantive dyestuffs and relatively attractive to basic dyestufis.

2. Method of modifying the dyeing prop- 105 erties of cellulosic fibers which consists in acting on the same with a phosphorous halogen compound capable of making the cellulosic fibers relatively immune to substantive dyestuffs and relatively attractive tobasic dyestuffs without previous mordanting.

3. Method of modifying the dyeing prop erties of cellulosic fibers which consists in alkalizing the fibers and treating the fibers with a phosphorous compound capable of making the cellulosic fibers relatively immune to substantive dyestuffs and relatively attractive to basic dyestuffs.

4. Method of modifying the dyeing properties of cellulosic fibers which consists in treating the fibers with a phosphorous halogen compound sufiioiently to make the fibers relatively immune to substantive dyestufi's and relatively attractive to basic dyestuffs and removing the halogen acid formed.

5. A cellulosic fiber in which more or less of the'cellulose is compounded with phosphorus and is capable of relatively resisting substantive dyestuffs and attracting basic dyestuffs.

aeeaeae 6. Method of modifying the dyeing properties of cellulosic fibers which consists in treating the same with a phosphorous halogen compound in the presence of an alkaline material.

7. Method of making fabrics with variegated colored effects which consists in forming the fabric with cellulosic threads, some only of which have been treated with a phosphorous compound to render them relatreated with substantive dyestuffs the so treated threads remain substantially unaf- Whereby the cellulosic fiber at the places so treated is rendered relatively immune to substantive dyestufis and relatively attractive to basic dyestuffs.

10. A fabric of cellulosic threads having certain portions thereof treated according to a predetermined design with a phosphorous halogen compound rendering the fiber of such treated portions relatively resistant to substantive dyestuffs and relatively attractive to basic dyestuffs without the previous use of a mordant whereby when the fabric is treated with substantive dyestufis they so treated threads remain substantially unaffooted.

11. Threads of cellulosic material in which the cellulose is compounded with phosphorus thereby rendering the threads substantially immune to substantive dyestuds.

12. Method of producing variegated designs on fabrics of cellulosic material which consists in printing a paste material on the fabric and exposing the fabric to the action of a phosphorous halogen compound locally according to a predetermined design.

13. Method of modifying the dyeing properties of cellulosic fibers which consists in treating the fibers with a phosphorous compound capable of making the cellulosi'c fibers relatively immune to substantive dyestuffs and relatively attractive to basic dyestuffs and also treating with an acid binding material.

In testimony whereof I. have signed my name to this specification.

ALBERT BODMER. 

